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3D/2D passivation as a secret to success
for polycrystalline thin-film solar cells
Deborah L. McGott,1,2 Christopher P. Muzzillo,1 Craig L. Perkins,1 Joseph J. Berry,1 Kai Zhu,1
Joel N. Duenow,1 Eric Colegrove,1 Colin A. Wolden,1,2 and Matthew O. Reese1,*

SUMMARY Context & scale

Polycrystalline photovoltaic materials offer low costs and good scal- Leading polycrystalline thin-film
ability; however, grain boundaries in these materials are extended technologies—cadmium telluride
defects, which can drastically increase carrier recombination. Inter- (CdTe), CuIn1-xGaxSe2 (CIGS), and
estingly, three leading polycrystalline thin-film technologies—cad- perovskite solar cells (PSCs)—are
mium telluride (CdTe), CuIn1-xGaxSe2 (CIGS), and perovskite solar based on very different materials,
cells (PSCs)—passivate absorber surfaces in the same way: via for- defect chemistries, and device
mation of low-dimensional, typically two-dimensional (2D), van der processing conditions, yet all
Waals materials. This has primarily occurred serendipitously achieve efficiencies rivaling that of
through process optimization, but in some cases, 2D capping layers crystalline silicon. We argue that a
are intentionally incorporated to improve device performance. previously unappreciated key to
Here, evidence compiled from the literature, supplemented with their shared success is passivated
new data where necessary, is presented to illustrate the existence (i.e., benign) surfaces via
of 3D/2D interfaces in CdTe, CIGS, and PSCs, and their correlation formation of two-dimensional (2D)
with improved passivation and device performance. This suggests van der Waals materials. In CdTe,
that 3D/2D passivation might be a heretofore unappreciated key the 2D material is CdCl2; in CIGS,
to successful polycrystalline thin-film photovoltaics. Finally, the it is XInSe2 (X = K, Rb, Cs) with X
desired attributes of successful low-dimensional layers are pre- depending on the heavy-alkali
sented with rational design strategies for next-generation polycrys- post-deposition treatment; and in
talline solar cells. lead halide PSCs, PbI2 forms
naturally, but many new, more
stable, 2D materials have recently
INTRODUCTION been incorporated. Importantly,
Leading thin-film photovoltaic (PV) technologies—cadmium telluride (CdTe), CuIn1- this work shows that the large
xGaxSe2 (CIGS), and perovskite solar cells (PSCs)—are polycrystalline with grain bound-
body of knowledge developed in
aries (GBs) that can substantially increase interfacial (surface) area. Surfaces represent PSCs on 3D/2D interface
discontinuities in the three-dimensional (3D) semiconductor lattice which can generate formation can, and should, be
large defect densities including strained and unterminated (‘‘dangling’’) bonds. These leveraged by other polycrystalline
physical defects introduce electronic defects and surface states that can mediate recom- technologies. In many cases, the
bination of electron-hole pairs and impair device performance. Dangling bonds also formation of 2D materials has
make surfaces energetically unfavorable and more reactive, resulting in chemical reac- been a consequence of empirical
tions that can create additional mid-gap states that further increase recombination. Sur- process optimization rather than
faces can be passivated (i.e., made benign) by (1) chemically reducing the number of by design. Here, we advocate for
recombination sites through surface reconstructions or adsorption of species that satisfy the active exploitation of 2D
local electron counting requirements or (2) electronically creating localized fields that materials and their highly tunable
reduce the number of carriers available to recombine at defect sites. If chemical passiv- properties both to further
ation is poor, the Fermi energy becomes pinned and electrical (field-effect) passivation enhance the performance of
is rendered ineffective. Thus, an ideal system is first chemically passivated and then uti- leading technologies and as a
lizes some form of field-effect passivation. strategy to elevate other
polycrystalline technologies that
All successful PV technologies employ some method(s) to passivate absorber sur- have underperformed to date
faces. In fact, improvements to surface passivation in silicon, the most dominant

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PV technology, have been key to enabling many record efficiencies over the past
seven decades.1 Leading polycrystalline thin-film technologies—CdTe, CIGS, and (e.g., GaAs). An important
PSCs—have not approached surface passivation as deliberately, but still obtain example of the tremendous
similar efficiencies2—how? We argue one reason is that absorber surfaces (inter- benefit that can be gained by
faces, GBs) in all three technologies are passivated via formation of low-dimensional, exploiting 2D material properties
typically two-dimensional (2D), van der Waals (vdW) compounds during is the greatly enhanced device
standard device processing. In CdTe, the 2D compound is CdCl2; in CIGS, it is stability of 3D/2D PSCs. By
XInSe2 (X= K, Rb, Cs) with X depending on the heavy-alkali post-deposition treat- outlining key attributes of
ment (PDT); and in lead halide PSCs, PbI2 forms naturally, but many new, more sta- successful 3D/2D systems along
ble, 2D perovskites have also been incorporated. 2D materials, which are typically with rational design strategies for
layer-stacked in their bulk/aggregate form, have naturally passivated surfaces owing implementation, we invite
to their weak vdW interlayer bonding which, when cleaved, leave little to no researchers of diverse
dangling bonds at the surface.3 Thus, when interfaced properly (e.g., via phase backgrounds—not just
segregation during device processing—see discussion for further details), the chem- photovoltaics but functionalized
ically passive surface of the 2D layer can be exploited by the 3D bulk. This offers a materials more generally—to
natural synergy (Figure 1) because 3D semiconductors, which typically have excel- consider how the advanced field
lent bulk properties (e.g., photogeneration, charge transport) owing to their high of 2D materials can be leveraged
crystallinity, can likewise benefit the 2D material, which typically has relatively in their unique system. Moreover,
poor bulk properties (charge transport, light absorption,4 dopability,5 contact this work presents an opportunity
resistivity6). for 2D-material researchers to
overcome some of their major
This paper demonstrates that despite being based on very different materials (Table challenges, such as
1), interfaces found in high-performance polycrystalline PV technologies share a commercialization, by leveraging
common feature: the presence of passivating 2D compounds. Generally, 2D interfa- the expertise of the photovoltaic
cial materials are present not by design, but instead have evolved from their 3D industry.
counterparts during device processing (Figure 2). In the next section, evidence is
presented for 3D/2D interface formation in CdTe, CIGS, and PSCs. This is then corre-
lated with improved passivation and device performance, particularly open-circuit
voltage (VOC), in the third and fourth sections, respectively. It is important to note
that although much of the evidence presented in this paper has been gleaned
from existing literature, and there is in fact a large body of literature for PSCs, the
significance of this perspective is to highlight that 3D/2D passivation occurs naturally
in all three of the highest-performing polycrystalline PV technologies and might have
played a role in their success. By drawing parallels between the three technologies,
we hope to demonstrate how the knowledge developed in each can, and should, be
leveraged by other technologies. In the discussion section, we outline key design
strategies such that 3D/2D passivation can be employed in polycrystalline PV
more generally. This is particularly important because each 3D material requires a
specific passivation approach.

Structural evidence for 3D/2D absorber interfaces

In this section, evidence is presented from the literature for 3D/2D interface forma-
tion in CdTe, CIGS, and PSC absorbers. Of these technologies, CdTe researchers
might be the most surprised by this claim. Although it is widely accepted that the
CdCl2 ‘‘activation’’ anneal (Figure 2A), a processing step crucial to CdTe’s success,
results in chlorine accumulation at absorber interfaces and GBs, chlorine is typically
considered only to passivate point defects. However, an X-ray photoelectron spec-
troscopy (XPS) study by Perkins et al.14 found that chlorine accumulated at the front
interface of superstrate CdS/CdTe devices was in the form of 2D CdCl2. In that study, 1National Renewable Energy Laboratory, Golden,

device stacks were cleaved at the SnO2/CdS interface via a novel low-temperature CO, USA
2Colorado
cleave technique which maintains interface chemistry. The thickness of the chlorine School of Mines, Golden, CO, USA
accumulation layer on either side of the cleave was measured with angle-resolved *Correspondence: matthew.reese@nrel.gov
XPS; each approximately matched one molecular layer of Cl-Cd-Cl (Figures 3A– https://doi.org/10.1016/j.joule.2021.03.015

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Figure 1. Natural synergy of 3D/2D PV systems

Shown are (left) crystal structures and (right) energy band diagrams for (top) a poorly passivated 3D
crystal with excellent bulk transport properties because of its highly crystalline nature and covalent
bonding and defective, reactive surfaces (red dangling bonds) which create mid-gap electronic
states that facilitate electron-hole recombination.
In the center is a 2D crystal with van der Waals interlayer bonding, resulting in chemically and
electronically passive surfaces but also poor bulk transport and charge extraction.
At the bottom is a 3D semiconductor with 2D surface passivation layers that eliminate dangling
bonds and offer type I band alignment, enabling efficient charge extraction.

3D). Rinsing the surfaces with water revealed the chlorine was bound in a water-sol-
uble, cadmium-containing compound. These findings, in conjunction with the
exceedingly uniform cleave over large areas (>1 cm2)24 and measurement of the
Cd 3d modified Auger parameter, led to the conclusion that the compound must
be 2D CdCl2. To validate this more generally, we performed similar studies using
state-of-the-art MgZnO (MZO)/Cd(Se,Te) devices. Cleavage occurred at the MZO/
Cd(Se,Te) interface (i.e., directly at the p-n heterojunction) again with evidence of
CdCl2 (Figures S1–S3). The MZO/Cd(Se,Te) device architecture is the subject of
new experimental findings presented in Sections 3 and 4.

It is possible that all CdTe absorber surfaces, including GBs, are terminated with 2D
CdCl2. However, there is currently insufficient evidence to draw strong conclusions
at GBs. Interestingly, the concentration and thickness of the chlorine layer at the
front interface (
20 at %,
7 Å)14 closely match what has been measured at GBs
(
14–60 at %, 1–2 nm).26–30 Moreover, first principle calculations have shown that
a defect complex commonly thought to decorate GBs, ClTe-VCd,31–33 has a structure

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Table 1. Comparison of leading polycrystalline thin-film PV technologies

CdTe CIGS PSCs
Device architecture p-n p-n p-i-n, n-i-p
Growth order superstrate substrate superstrate or substrate
Band-gap grading yes (recent) yes (historical) no
Composition II-VI I-III-VI2 organic/I-IV-VII3
Majority carrier p
1014 (historical, Cu)7 p
10169 p, n
1014–1016 10
concentration (cm3) p
1016(recent, As)8
Minority carrier 1–408,11 20–4009,12 150–2,00013
lifetime (ns)
2D materials CdCl214 KInSe2, KIn1-yGaySe2, examples: PbI2, (PEA)2PbI4,
identified RbInSe2, CsInSe215–18 (BA)2PbI44,19–21
Distinctions between CdTe, CIGS, and PSC technologies are important as follows: (1) growth order has
major implications on junction formation and allowable device processing; (2) band-gap grading allows
for more current and voltage extraction from a single junction device and until recently had only been
adopted by CIGS; (3) composition (i.e., constituents’ grouping in periodic table) affects ionicity, which
in turn affects defect type—compounds that are more ionic in character (e.g., CIGS and PSCs) tend to
have shallower defects with lower formation energies than compounds which are more covalent (e.g.,
CdTe); (4) until recent developments in group-V doping and Se-alloying, carrier concentration and life-
time in CdTe have historically been lower than CIGS and PSCs; note that CdTe and CIGS are p-type
whereas PSCs can be either p- or n-type, depending on the underlying layer, composition, and process-
ing22,23; (5) the presence of 2D materials are only beginning to be recognized in CdTe and CIGS, whereas
PSCs have explored numerous 2D materials, a few of which are noted in the table; other 2D perovskite
compounds are discussed in the referenced review articles.4,20,21 All referenced values in the table are
for completed polycrystalline devices.

approaching that of CdCl2.34 It is speculated that the reason CdCl2 has not
been directly observed at GBs—e.g., via transmission electron microscopy
(TEM),26,35–37—is because the special efforts needed to detect it, such as examining
the extended fine structure and coordination of chlorine (R.F. Klie, personal commu-
nication), have not been made. Finally, it is worth highlighting a point made by Per-
kins et al.14 which found that MgCl2, the only other material to produce similar ben-
efits to CdCl2,38,39 is also a 2D vdW compound.40

Like CdTe, state-of-the-art CIGS solar cells employ a PDT that has become a critical
part of device processing. Originally, a sodium-based PDT was used to dope CIGS
absorbers, but this has recently shifted to heavy-alkali PDTs (KF, RbF, and CsF) (Fig-
ure 2B) which have resulted in eight of the last ten world record CIGS cell effi-
ciencies.2,12,41–48 One possible reason for this dramatic improvement is that
heavy-alkali PDTs form 2D layered compounds (KInSe2, RbInSe2, and CsInSe2) at
absorber surfaces16,17,49,50 whereas the formation of NaInSe2 (which is also 2D) is
not thermodynamically favorable.16 The first direct evidence of 3D/2D interface for-
mation in CIGS occurred for RbF-treated films by Taguchi et al.16 In that study, scan-
ning TEM (STEM) revealed neat layers of 2D RbInSe2 with
5 nm thickness between
the CIGS absorber and CdS buffer (Figure 3E). TEM has also been used to demon-
strate the existence of 2D CsInSe2 layers at GBs in CsF-treated CIGS films.18 On the
other hand, the direct observation of 2D KInSe2 has proven difficult because of its
instability in air.49

2D compounds are also known to form at absorber surfaces in organic-inorganic

halide PSCs, both unintentionally and by design. Like CdTe and CIGS, the uninten-
tional formation of a 2D compound, PbI2 in this case,51 historically occurred in the
highest-performing devices, including tandem structures.52–56 It was found that by
adding a slight excess of PbI2 to the absorber precursor solution (Figure 2C), perfor-
mance could be improved.57–59 This has largely been understood to result from the

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Figure 2. Common introduction methods for naturally formed 2D materials

(A) 2D CdCl2 is standardly introduced to 3D CdTe absorber surfaces through a heated PDT.
(B) XInSe 2 (X= K, Rb, Cs; K shown here) is introduced via evaporation of heavy-alkali salt (KF, RbF, or CsF) in Se ambient after deposition of 3D CIGS film.
(C) PbI 2 naturally forms at 3D lead halide PSC surfaces (methylammonium lead iodide, MAPbI 3 , shown here) through the addition of excess PbI 2 to the
absorber precursor. 3D/2D PSCs have also been intentionally formed and are discussed throughout the text. Simplified 3D/2D grain boundary
structures are shown at the bottom for each technology. See Supplementary Note for a more detailed discussion of 2D layer formation at GBs.

degradation of 3D perovskites into PbI2 at absorber surfaces, creating a layer which

optoelectronically passivates,19,60–62 but also accelerates degradation via chemical
decomposition.63–65 Therefore, although 2D PbI2 forms naturally, it is an impractical
long-term solution. Instead, PSC researchers have turned to new 2D perovskite com-
pounds with significantly higher moisture and heat tolerance than their 3D counter-
parts.66–69 2D perovskites are commonly incorporated in two ways: (1) by performing
a PDT on the absorber surface before hole transport layer (HTL) deposition70–74 or (2)
mixing an additive into the absorber precursor that precipitates out to form 2D com-
pounds at GBs and interfaces.25,75–77 Of the many studies done, one by Tong et al.25
stands out for clear structural evidence from high-resolution TEM (HRTEM) (Fig-
ure 3F). In that study, guanidinium thiocyanate was added to a mixed tin-lead (Sn-
Pb) precursor, and a 2D, unidentified, layered structure was found to form at
absorber surfaces.

Optoelectronic evidence for 3D/2D surface passivation

Here, evidence from the literature, and new data, demonstrating the passivating effect
of 3D/2D interfaces is presented; the potential chemical passivation mechanisms are
explored in more detail in the discussion. Of the many optoelectronic techniques that
can probe recombination, we focus on time-resolved photoluminescence (TRPL)
because it is the only technique used to characterize 3D/2D passivation across all three
technologies. In particular, studies were chosen that attempted to isolate the effect of
either depositing or removing a single passivating layer of 2D material at an exposed
interface. Because these layers have only recently been discovered in CdTe and
CIGS, only one such study exists in CIGS and new data are presented for CdTe.

Using a process similar to Perkins et al.,14 MZO/Cd(Se,Te) devices were cleaved at

the MZO/Cd(Se,Te) interface (p-n heterojunction) where 2D CdCl2 was found to
accumulate (Figures S1–S3); CdCl2 was subsequently removed with a water rinse
in inert ambient. Figure 4A presents TRPL measurements taken before and after

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Figure 3. Evidence for 2D layer formation in CdTe, CIGS, and PSCs

(A–D) Shown are (A) angle-resolved XPS data from the SnO 2 and (B) CdS side of cleaved superstrate
CdS/CdTe device stacks, (C) 2D CdCl 2 chemical structure, and (D) schematic of CdCl 2 location
within CdTe device stack (used with permission from the American Chemical Society). 14
(E) STEM image of the CIGS/CdS interface in RbF-treated films demonstrating 2D layered RbInSe 2
formation (used with permission from the American Institute of Physics). 16
(F) HRTEM image of 3D Sn-Pb PSC grain boundary interfaced with a thin, unidentified 2D
compound (used with permission from the American Association for the Advancement of
Science). 25

cleavage and after CdCl2 removal. XPS spectra of water-rinsed CdTe show insignif-
icant changes in the extent of tellurium oxidation and oxygen adsorption (Figures
S3C and S3D), as expected from previous theoretical studies of chemical interac-
tions between CdTe and water.78 Therefore, the difference between the two cleaved
samples can primarily be attributed to the removal of CdCl2 passivation. The
decreased lifetime after cleavage can be caused by many factors including loss of
junction partner, change in strain state, and/or damage caused from cleaving
(e.g., microfracturing). A similar trend in TRPL was seen for CdS/CdTe devices which
were cleaved at, and CdCl2 was removed from, the SnO2/CdS interface (Figure S4).

Because of the novelty of heavy-alkali PDTs (KF, RbF, and CsF) in CIGS, few studies
exist which attempt to isolate 2D XInSe2 (X = K, Rb, Cs) surface passivation effects.

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Figure 4. Time-resolved photoluminescence evidence of 2D passivation in CdTe, CIGS, and PSCs

TRPL decay traces for:
(A) Superstrate MZO/Cd(Se,Te) device before (black) and after (red) cleavage at the MZO/
Cd(Se,Te) interface and after removal of the 2D CdCl 2 surface layer with a deionized (DI) water rinse
(blue). Lifetime (tau) values listed in the inset table (92 ns for as-grown, 20 ns for as-cleaved, and
15 ns for DI rinsed) were calculated as the slow decay term (t 2 ) of a biexponential fit.
(B) CuInSe 2 baseline (black), CuInSe 2 with copper-poor surface (red), and CuInSe 2 with 2D KInSe 2
surface layer (green), which had lifetimes of 8, 14, and 64 ns, respectively (used with permission from
Elsevier). 79
(C) MaPbI 3 films (16 ns lifetime untreated) that were then surface-treated with n-butylamine (BA) to
form 2D (BA) 2 PbI 4 (52, 122, and 204 ns lifetimes for 0.1, 0.3, and 1% v/v, respectively) or (D) n-
butylammonium iodide (BAI) to form 2D (BA) 2 (MA) n-1 Pb n I 3n+1 (48, 56, and 194 ns lifetimes for 1, 2,
and 4 mg/mL, respectively) (used with permission from the American Chemical Society). 80

One study that has, by Muzzillo et al.,79 used TRPL to examine differences in carrier
lifetime when 2D KInSe2 was grown on top of CuInSe2 films. Unlike typical CIGS, gal-
lium was omitted to confidently attribute observed trends to changes in potassium
rather than Ga/(Ga+In). KInSe2 was formed by quickly ramping the KF deposition
rate up while simultaneously ramping the Cu rate down at the end of film growth.
KInSe2 surface layers were verified via X-ray diffraction and secondary ion mass spec-
troscopy (SIMS) and measured to be
26–100 nm thick. This layer, although thick, is
expected to have a cation-intercalated layered structure.81 Figure 4B shows TRPL
curves for baseline CuInSe2, CuInSe2 with KInSe2 surface layer, and a copper-
poor-surface control. A clear difference in lifetime is seen for samples with and
without KInSe2. However, owing to the KInSe2 growth method, compositionally
graded intermediate layers might affect carrier lifetime. Therefore, although this
study provides good initial insight into the passivating effects of 2D KInSe2, further
research is required.

Unlike CIGS and CdTe, many studies in PSCs have examined passivation at 3D/2D
interfaces,70,74,25,76,77,80,82,83 including systems with PbI2.57,84–87 Of these studies,

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Figure 5. Device evidence of 2D passivation (VOC boost) in CdTe, CIGS, and PSCs
J-V curves for:
(A) MZO/Cd(Se,Te) devices before (solid markers) and after (open markers) being cleaved at the MZO/Cd(Se,Te) interface. Device 1 (black) was cleaved
and re-contacted. Device 2 (red) was cleaved, rinsed with DI water to remove CdCl 2 , and then re-contacted. Values listed in inset table are open-circuit
voltage (mV), short-circuit current density (mA/cm 2 ), fill factor (%), and efficiency (%), respectively.
(B) Buffer-free baseline CIGS (black), CIGS with K incorporated into the bulk (blue), and CIGS with 2D KIn 1-y Ga y Se 2 at the absorber/ZnO interface (green)
(adapted from Muzzillo and Anderson, 88 used with permission from Elsevier).
(C) 3D triple-cation Cs0.05 (FA0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 perovskite film with (orange) and without (black) 2D (PEA) 2 PbI 4 at the absorber/HTL interface
(used with permission from Wiley Online). 83

the ones that form 2D perovskites by using surface PDTs typically have the least ef-
fect on bulk properties and are the focus here. In a study by Lin et al.,80 3D MaPbI3
films were treated with two different solutions: n-butylamine (BA) dissolved in chlo-
robenzene and n-butylammonium iodide (BAI) dissolved in isopropanol. For BA-
treated films, pure 2D (BA)2PbI4 layers formed at the surface whereas BAI-treated
films exhibited a 2D perovskite mixture of (BA)2(MA)n-1PbnI3n+1 where n = 1 [i.e.,
(BA)2PbI4], 2, 3, and 4. In both cases, carrier lifetime improved with increasing con-
centration of BA or BAI, but BA-treated films were found to have slightly longer life-
times (Figures 4C and 4D). This was attributed to improved chemical passivation
from the conversion of defective 3D MaPbI3 into 2D perovskites.

Effects of 3D/2D passivation on device performance

It is well known that VOC, a critical performance parameter to all PV technologies, is
directly correlated with passivation quality. Simply, this is because decreased
recombination leads to greater excess carrier concentration in the absorber, thus
increasing quasi-Fermi-level splitting. Equivalently, as recombination increases,
dark (leakage) current increases and VOC decreases. The goal of this section is
to demonstrate that 2D materials, which were shown to exist at and passivate
CdTe, CIGS, and PSC absorber surfaces, are directly correlated with improved
VOC.

Looking first at CdTe, new data are presented in which superstrate MZO/Cd(Se,Te)
devices were cleaved at the p-n heterojunction [MZO/Cd(Se,Te) interface] and 2D
CdCl2 was selectively removed with water, resulting in no additional oxidation of
the Cd(Se,Te) surface (Figures S3C and S3D). Cleaved device stacks were recon-
structed with a MZO buffer, ZnO:Al front contact, and Ni/Al aperture. Figure 5A
demonstrates representative current density-voltage (J-V) curves for two devices
before and after cleavage. CdCl2 was removed from device 2, but not device 1.
Across the entire sample set, the average difference between as-cleaved and rinsed
samples was DVOC
40 mV, DJSC
not changed, DFF
13%, and DEff
2%. Similar
trends were found for cleaved CdS/CdTe devices (Figure S5).

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For CIGS, heavy-alkali PDTs have dramatically improved device performance,41,44,89,90

partly owing to considerable bulk changes.9,91,92 However, observed boosts in VOC are
consistently greater than expected from carrier concentration increases alone,90,91,93,94
suggesting that surface passivation must also play a role. This was confirmed in a study
where potassium was incorporated either into the CIGS bulk to form Cu1xK-
xIn1yGaySe2 or at the surface as 2D KIn1yGaySe2; both were then interfaced with
ZnO with no intermediate buffer (e.g., CdS).88 Figure 5B presents J-V curves for
buffer-free baseline CIGS, CIGS with 7 wt % potassium in the bulk, and CIGS with 2D
KIn0.7Ga0.3Se2 interface layer. Samples with the 2D layer showed clear improvements
in VOC, which was attributed to passivation of the CIGS surface and functional replace-
ment of the CdS buffer.

3D/2D passivation has also dramatically improved PSC performance, particularly in

regard to stability.25,70–76,82,83 That topic is discussed in detail elsewhere
though,4,21,95 and we instead focus on VOC improvements. Depending on the mate-
rials and introduction method used to form 3D/2D PSCs (e.g., additive versus surface
PDT), VOC is typically seen to increase by
30–200 mV.70–72,25,77,80,82,83 Here, we
focus on studies which use surface PDTs to form 2D perovskites at a single interface.
In one such study by Chen et al.,83 2D (PEA)2PbI4 was formed at the absorber/HTL
interface by spin coating a solution of phenylethylammonium iodide in isopropanol
and annealing at 100 C for 10 min, resulting in a VOC increase of
60 mV (Figure 5C).
Using Kelvin probe force microscopy, this improvement was attributed to the 2D
capping layer’s suppression of nonradiative recombination and increased Fermi-
level splitting between the absorber and passivation layer’s work functions.

DISCUSSION
In this manuscript, 2D layers have been shown to exist at and passivate absorber sur-
faces in the three leading polycrystalline thin-film PV technologies. We now analyze
key properties of 2D materials that make them successful in the hope of advancing
the next generation of solar cells. Briefly, successful passivating agents should:

(1) Terminate dangling bonds at the surface,

(2) Target dominant defect(s) (i.e., anion or cation),
(3) Not introduce mid-gap states relative to the absorber, and
(4) Incorporate easily using practical synthesis and deposition methods.

The first critical prerequisite is naturally satisfied by vdW compounds because of

their chemically passivated surfaces. However, dangling bonds will not be elimi-
nated simply by interfacing a vdW layer with a defective 3D crystal surface; the tran-
sition from 3D to 2D must also be passivated. One method introduces a (bulky) spe-
cies to target and occupy key vacancies, distorting the 3D structure until a 2D layer
phase segregates out—this is the case for the CIGS and PSC examples presented
above. Capping 3D crystals with 2D layers can also prevent dangling bonds by relax-
ing strain between grains and layers of dissimilar materials. Although 2D compounds
have been the most common and are therefore the focus of this paper, 1D and 0D
vdW materials, such as nanowires, nanotubes, fullerenes, and small molecules,
can satisfy this requirement as well. Such materials are already used in PSCs and
organic PV in many instances.96–98

When designing the chemistry of 3D/2D interfaces, the 2D compound should target
at least one of the dominant defects present in the 3D material (i.e., anion or cation),
whereas the best compounds will passivate multiple defect types. For example, in

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CdTe, Te-rich surfaces are known to exhibit significantly higher surface recombina-
tion than Cd-rich surfaces,99 making a Cd- or other group II-containing 2D com-
pound attractive, particularly when they satisfy local electron counting require-
ments.100 Studies have explored alternate Cl-containing compounds (e.g., Cl2 gas
and NaCl), but these typically result in voltage deficits of tens to hundreds of
mV.38,101 This suggests that of this class of materials, CdCl2 and MgCl2 are optimal
because they provide both cation to terminate Te-rich surfaces and halide to termi-
nate Cd dangling bonds. In CIGS, although the most harmful surface defect is still
debated, surfaces are often Cu-poor, leaving both Se and group III element(s)
with unsatisfied bonds.102 Large alkalis (K, Rb, and Cs) introduced during PDTs
target these bonds and phase separate to interfaces as 2D layers. In 3D hybrid pe-
rovskites with ABX3 structure (where A is an organic cation, B is a metal cation, and X
is a halide), the B-site cation (Pb2+ or Sn2+) is typically the source of degradation.103
By introducing bulky A-site cations, reactive BX2 species can be shielded from con-
tacting degradation catalysts (e.g., moisture) through steric hindrance. Some of the
most successful passivants include both cation and anion components [e.g., guani-
dinium (Gua+) and thiocyanate (SCN-)]25 to facilitate 2D phase formation. This
example highlights that although much of the pioneering work in 3D/2D PSCs has
focused on large ammonium compounds (e.g., BA+ and PEA+), each 3D bulk mate-
rial requires its own specific passivation approach.

In addition to chemically passivating surfaces, the 2D compound should not intro-

duce mid-gap states in the 3D semiconductor. This could be a reason for the lack
of success in passivation with NbSe2 for model CdTe systems,104–106 because tran-
sition-metal ions tend to produce deep-level defects in CdTe.107 If mid-gap states
are not introduced and the 2D compound has a band gap that is wider than the
3D semiconductor it is interfaced with, it might have the added benefit of enhancing
carrier extraction. This is likely the case for all 3D/2D systems presented throughout
this manuscript. Specifically, CdTe’s band gap is
1.4 eV108 whereas CdCl2’s is
5.8
eV109; CIGS has a band gap of 1.0–1.7 eV110 whereas KIn1-yGaySe2 has 2.71–3.22
eV,88 RbInSe2 has 2.0 eV,111 and CsInSe2 has 2.81 eV112; finally, PSCs’ standard
band gap is
1.6 eV113 whereas PbI2’s is
2.3 eV61 and more recent 2D perovskites
have even larger band gaps.77 This suggests at least part of the success of these 2D
materials lies in their ability to passivate chemically and via field effect. However,
many studies examining these systems focus solely on the field-effect aspect while
overlooking, or simply being unaware of, the chemical passivation provided by
the 2D materials. We argue that without proper chemical passivation, any beneficial
band bending would be inconsequential owing to Fermi-level pinning. Thus, it is the
chemical passivation which makes any field-effect passivation possible. It is noted
that wide-band-gap 3D semiconductors can also passivate interfaces via field effect;
however, chemical passivation using 3D materials generally requires epitaxial
growth and attention to lattice matching to avoid high densities of wrong or
dangling bonds at the interface.

As the final prerequisite, the passivating layer must form and be stable under prac-
tical conditions. This means the energy (i.e., temperature) required to form the
passivating layer should not be so high as to degrade the bulk 3D semiconductor.
In addition, the layer must be chemically and thermally stable to subsequent pro-
cessing and operating conditions, including moisture ingress in modules. Interest-
ingly, although 2D capping layers have enabled dramatic improvements in stability
for moisture-sensitive PSC bulk material, the inverse might be true for CdTe where
accumulation of water-soluble CdCl2 might create a weak, buried interface in other-
wise stable modules.14,78 The same might be true for CIGS,49,114 underlining the

1066 Joule 5, 1057–1073, May 19, 2021

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importance of optimizing 2D layer formation in CdTe and CIGS. Many ways exist to
introduce 2D materials, as demonstrated throughout the text, which can often begin
with a precursor that will subsequently dissociate and form 2D layers with the aid of
heat and/or solvents. In that case, the dissociation energy of the original compound
must also be considered. For example, in the studies which explore alternate Cl-con-
taining compounds in CdTe, only the compounds with the lowest dissociation en-
ergies were successful, likely for this reason.38,39 As previously discussed, both
CIGS and PSCs also require precursor materials that can easily dissociate and release
bulky cations to phase segregate as 2D layers.

It is important to recognize that the processes by which 2D materials are introduced

can also cause significant beneficial changes to the bulk. For CIGS, the PDT was orig-
inally employed as a way of introducing alkali dopants into samples grown on alkali-
free (plastic) substrates,115 and has subsequently been associated with improved
carrier concentrations,79 bulk passivation,15 and reduced potential fluctuations.9 In
the case of CdTe, CdCl2 is linked to many positive changes, including recrystalliza-
tion and grain growth,116,117 interdiffusion of the buffer (CdS or CdSe) and absorber
(CdTe),35,118,119 doping,120,121 and bulk passivation.122,123 For PSCs, the additive
approach to form 2D layers can affect nucleation and film growth of the
absorber,69,76,77 and post-deposition surface treatments can often lead to recrystal-
lization and domain growth.124 These types of bulk changes can also increase quasi-
Fermi-level splitting and VOC and are thus an important accompaniment of
incorporating 2D materials into 3D semiconductors and should be taken into careful
consideration when designing 3D/2D systems.

CONCLUSIONS
Despite being based on very different materials, three leading polycrystalline thin-
film PV technologies—CdTe, CIGS, and PSCs—all exhibit 3D/2D passivation. Of
the three technologies, 3D/2D PSCs are the most researched and have been used
as a powerful tool to overcome major device challenges such as stability. This dem-
onstrates that, if approached thoughtfully, 3D/2D passivation might be a key to
enabling next-generation thin-film solar cells, particularly if knowledge developed
by each technology is not siloed. Moreover, it might be the lack of 3D/2D passivation
which has hindered some polycrystalline technologies that are otherwise expected
to perform well, such as GaAs. Looking forward, as tandem solar cells become an
increasingly viable technology, 2D passivating layers are likely to play an important
role as tunnel junctions and/or contacting layers. For years, the rapid advancement
of 2D fabrication and characterization technologies has mirrored that of PV. Collab-
orative efforts from experts in 2D technologies and PV are now needed to rationally
implement this 3D/2D passivation design motif as a way to advance the field of poly-
crystalline PV, both in existing and emerging technologies.

METHODS
CdTe device fabrication and cleave process
CdTe solar cells were prepared in the superstrate configuration on commercial-
grade SnO2:F/SnO2-coated glass. 60 nm of Mg0.04Zn0.96O was deposited via radio
frequency magnetron sputtering in an oxygen/argon ambient. CdSe (150 nm) and
CdTe (250 nm) were thermally evaporated at substrate temperatures of 450 C–
500 C. A thick layer of CdTe (
4 mm) was then deposited via vapor transport depo-
sition at similar temperatures. A vapor-phase CdCl2 anneal was then performed at
temperatures of 420 C–450 C. Samples were then soaked in 0.1 mM CuCl2 and an-
nealed at 200 C–220 C, and Au pads (5 3 5 mm2) were deposited via thermal

Joule 5, 1057–1073, May 19, 2021 1067

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Perspective

evaporation. It is noted that this device architecture results in high-performing

Cd(Se,Te) devices for Cu defect chemistries and are from a baseline process that
generally produces 16% to 17% efficient devices, but can achieve as high as 19%.
This architecture is representative of what is found in the literature for record effi-
ciency devices. As discussed earlier, other architectures, including the older CdS/
CdTe and emerging group-V-doped Cd(Se,Te) architectures, exhibit similar signa-
tures of 3D/2D passivation. After completion of the as-grown superstrate Cd(Se,Te)
devices, J-V measurements were performed and another Au layer, a uniform blanket
coating, was deposited. The purpose of the second layer was to create a large area
of contact for cleaved devices and to aid in delamination.

Samples were cleaved by adhering a small brass plate (
6 cm3) to the back side of the
CdTe device stack using Hysol 1C epoxy and curing at room temperature overnight. In a
nitrogen-filled glovebox, epoxied samples were then submerged into a bath of liquid
nitrogen where they spontaneously cleaved at the MZO/Cd(Se,Te) interface in the loca-
tions of the original 5 3 5 mm2 Au pads. Everywhere else (i.e., surrounding the original
device area in the superstrate configuration), the stack cleaved at the Au-blanket/
Cd(Se,Te) interface such that Au was exposed everywhere surrounding the devices (Fig-
ure S1). Cleaved samples were then extracted from the bath into a stream of dry nitrogen
gas until room temperature was reached. Still in the nitrogen ambient, half of the cleaved
samples were rinsed in vacuum de-gassed DI water for 15 s to remove the CdCl2 layer.
Samples were extracted into a stream of dry nitrogen gas until dry.

To complete the cleaved device stack, Shipley S1818 photoresist was applied in an
inert ambient to mask the exposed Au. Samples were then transported in a nitrogen-
filled container to a sputter chamber in which 120 nm of Mg0.04Zn0.96O was depos-
ited in an oxygen/argon ambient. This was followed by 120 nm of ZnO:Al in a sepa-
rate sputter chamber. Because ZnO:Al has a much higher sheet resistance than the
original SnO2:F (
60 U/sq compared with
13 U/sq), a Ni/Al aperture was deposited
to aid in current collection. It is worth noting that the
15% efficient cleaved
Cd(Se,Te) devices presented in Figure 5A are in the substrate configuration and
can be made lightweight and flexible, as outlined by McGott et al.24

Characterization
TRPL measurements were taken by using an experimental setup similar to that
described by Kuciauskas et al.125 Short pulses were provided by a PicoQuant
670 nm diode laser and driver with variable intensity and repetition rate. A repetition
rate of 1 MHz and power of 7 mW was used to generate an injection level of
5e16
photons per second for CdTe, given a laser beam spot size of 50 mm. A fiber-coupled
avalanche photodiode with timing resolution of 40 ps was used as the detector.
Instrument response function was measured to be
130 ps. Micrometers on the
sample stage allowed TRPL measurements taken after each processing step (i.e.,
as-grown, cleaved, DI rinsed) to be taken in the same locations for each device. Biex-
ponential fits were taken over the decay portion of the TRPL curves, and the slower
decay rate (t 2 ) was extracted.

J-V measurements were made under standard test conditions (1,000 W m2, 25 C,
and AM1.5G) in the superstrate configuration for as-grown samples (solid markers in
Figure 5A) and substrate configuration for cleaved samples (open markers). For this
reason, there were additional shadowing losses from the Ni/Al aperture in cleaved
devices, which were accounted for using the simple formula developed by Kier-
masch et al.126:

1068 Joule 5, 1057–1073, May 19, 2021

 ll
Perspective

nkT AAperture
DVOC = ,lnðXÞ with X = ; (Equation 1)
q ADevice
where n is the diode ideality factor, kT/q is the thermal voltage, AAperture is the area of
the hole opening in the aperture, and ADevice is the total device area. Ideality factor
was determined by measuring VOC as a function of light intensity (Figure S6). Sample
sets for each processing condition (i.e., as-grown, cleaved, DI rinsed) consisted of

16 devices. Average losses were calculated by measuring the loss for each device
owing to its particular processing (i.e., cleave or cleave with DI-rinse) and averaging
across the given sample set.

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.joule.
2021.03.015.

ACKNOWLEDGMENTS
The authors would like to thank Dr. Lorelle Mansfield for modeling efforts to support
this work, which ultimately were not fruitful, and Prof. Robert Klie for insightful dis-
cussion regarding CdCl2 detection via TEM in CdTe. This work was supported by
the United States Department of Energy under contract number DE-AC36-08-
GO28308 with Alliance for Sustainable Energy, LLC, manager and operator of the
National Renewable Energy Laboratory. Funding was provided by the United States
Office of Naval Research under agreement IAG-16-02002 and the United States
Department of Energy Office of Energy Efficiency and Renewable Energy Solar En-
ergy Technologies Office under agreements 34346, 34352, and 34353. The views
expressed in the article do not necessarily represent the views of the Department
of Energy or the United States government. The United States government retains
and the publisher, by accepting the article for publication, acknowledges that the
United States government retains a nonexclusive, paid-up, irrevocable, worldwide
license to publish or reproduce the published form of this work or allow others to
do so, for United States government purposes.

AUTHOR CONTRIBUTIONS
D.L.M. performed the new CdTe experiments and wrote the manuscript. C.P.M. pro-
vided technical discussion and review of the CIGS sections, made Figure 1 and Table
1, and wrote an early version of the manuscript. J.J.B. and K.Z. provided technical
discussion and review of the perovskite sections. J.N.D. and E.C. grew the MZO/
Cd(Se,Te) devices, and E.C. made Figure S6. C.A.W. provided edits and technical
discussion for the entire work. C.L.P. and M.O.R. originated the concept of 3D/2D
passivation across PV technologies and provided edits and technical discussion
for the entire work. M.O.R. wrote the discussion section. C.L.P. performed XPS ex-
periments in supplemental information.

DECLARATION OF INTERESTS
The authors declare no competing interests.

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